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  • Siloxysilylaminosilanes  (1)
  • Wiley-Blackwell  (1)
  • 1
    ISSN: 0044-2313
    Keywords: Siloxysilylaminosilanes ; siloxysilylamidosilanes ; cyclodisilazanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Lithiated Siloxy-silylamino-silanes  -  Preparation and Reactions with ChlorodimethylsilaneThe siloxy-silylamino-silanes (Me3SiO)Me3-nSi(NHSiMe3)n (1: n = 1, 2: n = 2, 3: n = 3) are obtained by coammonolysis of the chlorosiloxysilanes (Me3SiO)Me3-nSiCln (n = 1-3) with chlorotrimethylsilane.The reaction of 1, 2, and 3 with n-butyllithium in appropriate molar ratio in n-hexane gives the siloxy-silylamido-silanes (Me3SiO)Me3-nSi(NLiSiMe3)n (4: n = 1, 5: n = 2, 6: n = 3), which were spectroscopically characterized (IR, 1H-, 7Li-, 29Si-NMR) and allowed to react in solution (n-hexane, THF) with Me2Si(H)Cl.4 reacts to the N-substitution product (Me3SiO)Me2SiN(SiMe3)SiMe2H 7, 5 to (Me3SiO)MeSi[N(SiMe3)SiMe2H](NHSiMe3) 8, (Me3SiO)MeSi[N(SiMe3)SiMe2H]2 9 and to the cyclodisilazane 10. 6 gives in THF the cyclodisilazanes 11: R = H; 12: R = HMe2Si) and ( 13, in n-hexane only 11 in small amounts. An amide solution of 2 with n-butyllithium in the molar ratio 1:1 in n-hexane leads to 8 (main product), 2 and 10; in THF 10 and 2 are obtained nearly in same amounts and 8 and 9 as byproducts. The amide solutions of 3 with n-butyllithium in the molar ratio 1:1 and 1:2, resp., show nearly the same behaviour in n-hexane and THF. In THF 3, 11, and 12 and in n-hexane 3, 11, 12, and (Me3SiO)Si[N(SiMe3)SiMe2H](NHSiMe3)2 14 are formed.
    Notes: Durch Koammonolyse der Chlorsiloxysilane (Me3SiO)Me3-nSiCln (n = 1-3) mit Chlortrimethylsilan wurden die Siloxy-silylamino-silane (Me3SiO)Me3-nSi(NHSiMe3)n (1: n = 1, 2: n = 2, 3: n = 3) dargestellt.Die Reaktion von 1, 2 und 3 mit n-Butyllithium im jeweils erforderlichen Molverhältnis in n-Hexan ergibt die Siloxy-silylamido-silane (Me3SiO)Me3-nSi(NLiSiMe3)n (4: n = 1, 5: n = 2, 6: n = 3), die spektroskopisch (IR, 1H-, 7Li-, 29Si-NMR) charakterisiert und in Lösung (n-Hexan und Tetrahydrofuran) mit Me2Si(H)Cl umgesetzt wurden.4 reagiert zum N-Substitutionsprodukt (Me3SiO)Me2SiN(SiMe3)SiMe2H 7, 5 zu (Me3SiO)MeSi[N(SiMe3)SiMe2H](NHSiMe3) 8, (Me3SiO)MeSi[N(SiMe3)SiMe2H]2 9 und zum Cyclodisilazan 10. 6 gibt in THF die Cyclodisilazane (11: R = H; 12: R = HMe2Si) und 13, in n-Hexan nur 11 in geringen Mengen. Eine Amidlösung aus 2 mit n-Butyllithium im Molverhältnis 1:1 führt in n-Hexan zu 8 (Hauptprodukt) sowie zu 2 und 10, in THF entstehen 10 und 2 in annähernd gleichen Teilen sowie als Nebenprodukte 8 und 9. Amidlösungen aus 3 mit n-Butyllithium-im Molverhältnis 1:1 bzw. 1:2 zeigen in n-Hexan und THF annähernd gleiches Verhalten. In THF werden 3, 11 und 12 und in n-Hexan 3, 11, 12 und (Me3SiO)Si[N(SiMe3)SiMe2H](NHSiMe3)2 14 gebildet.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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